Higher aluminum alkyls and products therefrom



United States Patent ()1 HIGHER ALUMINUM ALKYLS AND rnonucrs THEREFROM Frank XhWerb'er, Kensington, and Frank A. Mirabile, Silver Spring, Md., assignors to W. R. Grace & 60., Clarksville, Md., a corporation of- Connecticut No Drawing-. Filed June 29, 1959, Ser. No. 823,285

7 Claims. (Cl. 260-448) This invention relates a novel method of forming aluminum alkyls containing at least one n-octyl group and products therefrom.

summarily, this invention is directed to the formation of aluminum alkyls containing at least one n-octyl group by a displacement reaction between octene-2 and aluminum triisobutyl in the presence of a cobalt chloride catalyst at substantially atmospheric pressure. The thusformed n-octyl containing aluminum alkyls can be converted to octanol-l by oxidation and hydrolysis.

It is known to react butene-Z in the presence of cocatalysts consisting essentially of aluminum triethyl and finely divided nickel or nickel salts under pressures of 50-500 atmospheres. See German patent application F12426, IVB, 120, K. Ziegler et al. Such a process requires costly high pressure resistant equipment and the product obtained from said reaction is a dimer, i.e., 2-ethylhexene-1.

Surprisingly, we have now found that subjecting octene- 2 to the action of at least a stoichiometric amount of aluminum triisobutyl in the presence of a cobalt chloride catalyst at substantially atmospheric pressure and a temperature of 25-150 C. results in the formation of aluminum alkyls containing at least one n-octyl group.

The thus-formed aluminum alkyls on subsequent oxidation and hydrolysis are converted to octanol-l.

The displacement reaction is operable at temperatures ranging fromroom temperature to 150 C., preferably 70-410 C.

The displacement reaction is performed at substantially atmospheric pressure, preferably under a blanket of an inert gas selected from the group consisting of nitrogen and the noble gases. The presence of the inert gas is to insure the exclusion of oxygen-containing substances which retard or preclude the displacement reaction.

The amount of CoCl catalysts is not critical. Relatively small amounts are adequate to catalyze the reaction. In general, a coCl ztriisobutyl aluminum mole ratio of 1:10 to 200 respectively is operable, preferably 1:100 is used. Larger amounts of CoCl can be employed but are unnecessary.

The quantity of octene-2 should be at least the stoichiometric amount necessary to react with the triisobutyl aluminum. Thus an aluminum triisobutyl: octene-Z mole ratio of 1:3 to 10 respectively is operable, preferably 1:3 to 5 is employed.

In converting the aluminum alkyls containing at least one n-octyl group into alcohols the oxidation step is preferably performed after cooling the reaction products of the displacement reaction to room temperature. Since the addition of oxygen to the displacement reaction product causes an exothermic reaction, it is preferred to initially add the oxygen slowly and then increase the rate of addition as the reaction progresses. In the oxidation .sarily carried out under pressure.

The hydrolysis-step may be performed under the same conditions of temperature and pressure as the oxidation step but is.- preferably carried out at room temperature and atmospheric pressure. Although HCl is used as the hydrolysis reagent in the examples, any hydrolysis reagent which is capable of hydrolyzing aluminum alcoholates can be employed.

The following examples will aid in explaining, but in no way limit the invention. In the examples, all equipment was dried at 100 C. in a drying oven overnight. Prior to use the system was heated to 100 C. and flushed with nitrogen for one-half hour. The reaction system consists of a three necked flask with a thermometer well, dropping funnel, gas inlet tube and a water-cooled condenser removably connected to a Dry Ice-isopropanol cooled condenser. The condensate (isobutylene) from the displacement reaction after. passing through the afore said condensers is collected in a graduated receiver immersed' in a Dry Ice isopropanol bath.

The analysis of the fractions obtained in Examples 1 and 2 were identified by a combination of gas liquid phase chromatography and infra-red spectra. The gas liquid phase chromatography analysis were made on a Perkin- Elmer Model 1548 Vapor Fractometer by comparing the retention time of the fractions with commercially available isobutyl alcohol, octene-2, octanol-l and octanol-2, which were employed as standards. The infra-red spectra of the aforesaid standards were then compared to the fractions to confirm identification on a Perkin-Elmer Model 21 Infra-red Spectrophotometer. The analysis of the fractions appear in the analysis column under the appropriate method of analysis in the examples.

Example I To a three neeked reaction flask was added 0.089 mole aluminum triisobutyl (17.6 grams), 0.26 mole octene-Z (30.7 grams) and 0.00089 mole of CoCl The reaction mixture was heated to C. at which temperature isobutylene was evolved andcollected in the cooled graduated receiver. The temperature range during the reaction was fro-m 70102 C. At the end of 5 hours the displacement reaction was discontinued. The displacement reaction went to 64% completion as measured by the isobutylene collected in the graduated receiver.

The remaining mixture containing the reaction prod ucts of the displacement reaction, excepting isobutylene, was diluted with 250 cc. of cyclohexane and cooled in an ice-salt water bath to about 5 C. At that time, oxygen was bubbled through the reaction mixture for a period of 24 hours to insure complete oxidation. The resulting alcoholates were hydrolyzed by adding cc. 10% HCl to the reaction flask and stirring for 5 hours. The contents of the reaction flask was then transferred to a separatory funnel wherein the organic layer was separated from the aqueous layer. The organic layer containing the thus-hydrolyzed alcoholates was dissolved in 100 cc. of other at room temperature and dried under anhydrous K CO for 24 hours to remove any residual water and to neutralize the acid. The solution was then filtered and the filtrate distilled at atmospheric pressure and a temperature of 3540' C. to remove the ether solvent. The residue from this distillation was subjected to a further distillation under a reduced pressure of 20 mm. Hg to obtain the following fractions:

The percent overall conversion to octanol-l based on octcne-2 was 18.25%.

The necessity of the presence of CoCl in the reaction to obtain octanol-l from octene-2 is shown by the following example:

Example 11 Using the equipment and procedure of Example I, 0.089 mole aluminum triisobutyl and 0.26 mole octene-2 was added to the three-necked reaction flask and heated to 95 C. at which temperature isobutylene was evolved and collected in the cooled graduated received. The run was continued for 5 hours during which time the temperature ranged between 70 and 105 C. At the end of the 5 hour period the displacement reaction went to 40% completion as measured by the isobutylene collected in the cooled graduated receiver. The remaining mixture containing the reaction products of the displacement reaction, excepting isobutylene, was diluted with 250 cc. of cyclohexane and cooled in an ice-salt water bath to about 5 C. Oxygen was then bubbled through the reaction mixture for 24 hours. The resulting alcoholates were hydrolyzed by adding 100 cc. HCl to the reaction flask with agitation for one hour. The contents of the reaction flask were then transferred to a separatory funnel wherein the organic layer was separated from the aqueous layer. The organic layer containing the thushydrolyzcd alcoholates was dissolved in 100 cc. of ether at room temperature and dried under anhydrous K CO for 24 hours to remove any residual water and to neutralize the acid. The solution was then filtered and the filtrate distilled at a temperature of 3540 C. and atmospheric pressure to remove the ether solvent. The residue from this distillation was subjected to a further distillation at atmospheric pressure to obtain the following fractions:

As can be seen from comparing Examples I and II, the presence of the catalyst CoCl is necessary in order to obtain primary alcohol, i.e. octanol-l from an octene-2 reactant. The aluminum alkyls containing at least one n-octyl group prepared by the process of this invention are useful as intermediates in making octanol-l.

The octanol-l can be esterified with a variety of readily available dibasic acids such as phthalic, isophthalic, adipic pimelic, azelaic, sebacic acids and the like to give dioctyl esters useful as plasticizers for vinyl resins and lubricants.

We claim:

1. The process of making aluminum alkyls containing at least one n-octyl group that comprises reacting octene-2 with at least a stoichiometric amount of aluminum triisobutyl in the presence of a CoCl catalyst at a temperature of 25-150 C. and substantially atmospheric pressure.

2. The process according to claim 1 wherein the aluminum triisobutylzoctene-Z mole ratio is 1:3 to 10 respectively.

3. The process according to claim 1 wherein the temperature is -125 C.

4. The process according to claim 1 wherein the reaction is performed under a blanket of an inert gas selected from the group consisting of nitrogen and the noble gases.

5. The process that comprises reacting octene-2 with at least a stoichiometric amount of aluminum triisobutyl in the presence of a CoCl catalyst at substantially atmospheric pressure thereby forming aluminum alkyls containing at least one n-octyl group, subjecting the n-octyl containing aluminum alkyls to a member of the group consisting of oxygen and air to form alcoholates, hydrolyzing the alcoholates and recovering octanol-l.

6. The process according to claim 5 wherein the aluminum triisobutyl:octene-2 mole ratio is 1:3 to 10 respectively.

7. The process according to claim 5 wherein the aluminum alkyls are formed under a blanket of an inert gas selected from the group consisting of nitrogen and the noble gases.

References Cited in the file of this patent UNITED STATES PATENTS 2,695,327 Ziegler et al Nov. 23, 1954 2,835,689 Ziegler et al May 20, 1958 2,863,895 Kirshenbaum Dec. 9, 1958 

1. THE PROCESS OF MAKING ALUMINUM ALKYLS CONTAINING AT LEAST ONE N-OCTYL GROUP THAT COMPRISES REACTING OCTENE-2 WITH AT LEAST A STOICHIOMETRIC AMOUNT OF ALUMINUM TRIISOBUTYL IN THE PRESENCE OF A COCL2 CATALYST AT A TEMPERATURE OF 25-150*C. AND SUBSTANTIALLY ATMOSPHERIC PRESSURE. 